CN103154203A

CN103154203A - Integrated process for steam cracking

Info

Publication number: CN103154203A
Application number: CN2011800337560A
Authority: CN
Inventors: S·M·戴维斯; R·C·斯特尔; 刘俊贤; S·H·布朗; P·F·柯森科思恩; A·R·迪尼克兰托尼奥; J·J·瓦尔德洛普
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2010-07-09
Filing date: 2011-06-09
Publication date: 2013-06-12
Anticipated expiration: 2031-06-09
Also published as: SG186124A1; WO2012005861A1; CN103154203B

Abstract

This invention relates to a process and system for cracking hydrocarbon feedstock containing vacuum resid comprising: (a) subjecting a vacuum resid to a first thermal conversion in a thermal conversion reactor (such as delayed coker, fluid coker, FlexicokerTM, visbreaker and catalytic hydro visbreaker) where at least 30 wt% of the vacuum resid is converted to material boiling below 1050 DEG F (566 DEG C); (b) introducing said thermally converted resid to a vapor/ lquid separator, said separator being integrated into a steam cracking furnace, to form a vapor phase and liquid phase; (c) passing said vapor phase to the radiant furnace in said steam cracking furnace; and (d) recovering at least 30 wt% olefins from the material exiting the radiant furnace (based upon the weight of the total hydrocarbon material exiting the radiant furnace).

Description

The integration method of steam cracking

The contriver: the SM Davis, RC Si Teer, Liu Junxian, SH Blang, Ke PF Sen Kesien, AR Di Nike Lantonio, and JJ Grindelwald Lip river is general

Relevant priority application

The application advocates the USSN12/833 that on July 9th, 2010 submits to, the right of priority of the EP application No.10177302.6 submitted on September 17th, 556 and 2010, and its disclosure is incorporated to by reference with its integral body.

Quoting of related application

The application relates to the application USSN12/833 that simultaneously has submission, 485 (lawyer's files numbering 2010EM008) (submissions on July 9th, 2010).The application also relates to the USSN12/692 of submission on January 22nd, 2010,222 (lawyer's files numbering 20/10EM009).

Technical field

The present invention relates in steam cracker furnace or pyrolysis oven by crude oil or prepare the method for alkene containing the crude oil fractions of residual oil.

Background technology

The thermally splitting of hydrocarbon is a kind of petrochemical process of producing alkene (for example ethene, propylene, butylene, divinyl) and aromatic hydrocarbon (for example benzene, toluene and dimethylbenzene) that is widely used in.These each is because itself being all valuable industrial goods.For example, described alkene can be oligomeric (for example, form lubricant base), polymerization (for example, form polyethylene, polypropylene and other plastics), and/or functionalization (for example, forming acid, alcohol, aldehyde etc.), all these have well-known intermediate and/or end-use.

Steam cracking (also referred to as pyrolysis), already for various hydrocarbon feeds are cracked into to alkene, preferred light olefin is ethene, propylene and butylene for example.Usually, for the raw material of steam cracking be such as petroleum naphtha, gas oil or other containing the whole crude cut of residual oil, its can be for example by distillation or otherwise the fractionation whole crude obtain.The steam cracker furnace with two major sections is used in conventional steam cracking: convection zone and radiation section.Described hydrocarbon feed typically enters the convection zone (except the lightweight material entered as steam) of this stove as liquid, wherein this hydrocarbon feed usually by the hot flue gases indirect contact with from radiation section with by with steam, directly contacting and be heated and gasify.Then, raw material (with the optional steam) mixture of gasification is sent to the radiation section that cracking occurs.Usually, the mixture of gasification is incorporated into to radiation section by cross manifold, wherein the mixture of this gasification approximately is being heated to harsh hydrocarbon cracking temperature under the pressure of 10 to about 50psig (69-345kPa) scope usually rapidly, for example approximately 1450 ℉ (788 ℃) to the about scope of 1650 ℉ (900 ℃), with the thorough thermally splitting of the stream of supplying raw materials.The product that comprises the gained of alkene leaves steam cracker furnace to carry out further Downstream processing.

After cracking, from the effluent of pyrolysis oven, comprise multiple hydrocarbon gas, for example, saturated, cholesterol and polyunsaturated hydrocarbon, and can be aliphatics and/or aromatic hydrocarbon, and the molecular hydrogen of significant quantity.The product of cracking is for example usingd and is produced the individual material of multiple highly purified separations and flow as the equipment product by further processing subsequently in olefin production plant, i.e. hydrogen, light olefin ethene, propylene, butylene and aromatic compound and other product pressure gasoline for example.

Exhaustion along with the operability in the increase to the light olefin widespread demand and favourable crude oil source, therefore be necessary to utilize the crude oil of heavy more (, there are those of residual oil more at high proportion), it requires capital investment of increasing with processing and processes the by product of refining.Wish very much can adopt more low-cost, the more crude oil of heavy and the method for more effectively producing the Product mix of more favourable light olefin.Yet the process for steam cracking of known conventional is easy to be contained the even raw material serious scale of the residual oil of small concentration, described residual oil exists usually in the inferior quality heavy feedstocks.Therefore, most of steam cracker furnace are restricted to the more processing of high quality raw material, and described more high quality raw material has basically made all residue oil fractions remove in other refining process.These extra processes have increased the cost of holistic approach.Similarly, residue oil fraction remove the total transformation efficiency that has reduced refining process because most of residue oil fraction mixes with low value oil fuel, rather than change into the more material of high value.

The disclosed patent application No.2007/0090018 of United States Patent (USP), be incorporated to this paper by reference, discloses the integration of hydrotreatment and steam cracking.To comprise that crude oil or its are containing the charging of residue oil fraction hydrotreatment and pass into steam cracker to obtain olefin product harshly.

The cracking of heavy hydrocarbon charge in fluid coker has been described.For example, U.S. Patent No. 3,671,424, be incorporated to this paper by reference, discloses a kind of two-stage fluidized coking process, and wherein the first step is that transfer line and the second stage of short contacting time are transfer line or fluidized-bed.

The important extension that the use of the separating tank of integrating with steam cracker furnace has developed into this platform is with the raw material that allows to process heavy more long residuum for example.But described separating tank provides a kind of means to separate the heaviest component and prevent the heaviest cut fouling in steam cracker furnace that comprises pitch type molecule from the cracked gasoil molecule.Unfortunately, by using this method, most of heavy vacuum residuum molecules (it is favourable due to lower cost as raw material) still transform in liquid phase and not in the radiation section of steam cracker furnace.

Other important patent comprises US7,097,758; US7,138,047; US7,193,123; US3,487,006; US3,617,493; US4,257,871; US4,065,379; US4,180,453; US4,210,520; US3,898,299; US5,024,751; US5,413,702; US6,210,561; US7,220,887; US2007/023845; WO01/66672; WO2007/117920; US6,632,351; US4,975,181; WO2009/025640;

US2007/0090018 and WO2007/117919.Other important document comprises: " Tutorial:Delayed Coking Fundamentals. " P.J.Ellis and C.A.Paul, article 29a, Topical Conference on Refinery Processing, 1998Great Lakes CarbonCorporation (it can be downloaded from http://www.coking.com/DECOKTUT.pdf).

In this area, still exist process economically heavy containing the charging of residual oil so that produce alkene,

The new tool of aromatic hydrocarbons and other valuable petrochemicals and the demand of improved method.Similarly, still exist in this area residual oil is upgraded to the more useful and/or demand of compositions useful more.

The invention discloses a kind of method of being produced in the following manner chemical preparations by heavy feed stock,

Wherein the vacuum residuum of signal portion is converted into to the more molecule of lightweight, described lighter molecule can easierly gasify and be subsequently converted to fuels and chemicals in separating tank.

Summary of the invention

The present invention relates to the method for the hydrocarbon feed that cracking comprises residual oil, the method comprises:

(a) hydrocarbon feed that will contain vacuum residuum is sent to the first thermal transition district, wherein by described heating raw materials to the temperature that is less than 649 ℃ (1200 ℉), wherein at least the vacuum residuum of 30wt% is converted into below 566 ℃ (1050 ℉) material of boiling;

(b) residual oil of described thermal transition is incorporated into for example, in gas/liquid separation (separating tank) to form gas phase and liquid phase, described separator be connected with the steam cracker furnace fluid (for example, being incorporated into steam cracker furnace);

(c) described gas phase is sent to the radiant-type furnace in described steam cracker furnace; With

(d) by the salvage material of the leaving radiant-type furnace alkene of 30wt% (weight of the total hydrocarbon material based on leaving radiant-type furnace) at least.

In another embodiment, the method for the hydrocarbon feed that the present invention relates to comprise residual oil for cracking, the method comprises:

(a) heat packs is containing the hydrocarbon feed of residual oil;

(b) hydrocarbon feed of described heating is sent to gas/liquid separation (for example separating tank);

(c) liquid phase of the hydrocarbon feed of the described heating of flash distillation to form gas phase and to comprise described residual oil in described separator;

(d) will be sent to from least a portion of the described liquid phase that comprises residual oil of described separator below 649 ℃ (1200 ℉) operation and optionally comprise the thermal conversion reaction device of coke granule;

(e) liquid phase that comprises residual oil of described thermal transition is sent to gas/liquid separation (for example separating tank) to form the second gas phase and second liquid phase, described separator be connected with the steam cracker furnace fluid (for example, being incorporated into steam cracker furnace);

(f) described the second gas phase is sent to the radiant-type furnace in described steam cracker furnace; With

(g) by the salvage material of the leaving radiant-type furnace alkene of 30wt% (weight of the total hydrocarbon material based on leaving radiant-type furnace) at least.

In another embodiment, the liquid phase of leaving the first gas/liquid separation is further heated to for example temperature of 1000-1200 ℉ (538-649 ℃), usually in the low coil pipe of the convection zone of steam cracker, usually the material of part heating is usually by viscosity breaking, for example, in water (steam) quenching thereafter the gasification reaction material of viscosity breaking, the viscosity breaking material of described gasification is sent to the second gas/liquid separation subsequently, wherein the material separation of viscosity breaking is become to liquid and gas.Subsequently gas phase is incorporated into steam cracker (at convection zone or at radiation section) and wherein at least the alkene of 30wt% reclaim (weight of the total hydrocarbon material based on leaving radiant-type furnace) from the material that leaves radiant-type furnace.

Favourable, the initial hydrocarbon raw material usually comprise between 10wt% and 50wt% at 566 ℃ ⁺the residual oil of boiling, preferred about 20-40wt%, and method described herein makes this residual oil of height ratio can be converted into chemical.

In preferred embodiments, from the liquid that comprises residual oil of the second gas/liquid separation, further do not process with production of chemicals.Replace, this material is preferably used as the blending stock that adds oil fuel or processes to produce fuel for further refining.

In preferred embodiments, the method for the hydrocarbon feed that the present invention relates to comprise vacuum residuum for cracking comprises:

(a) heat packs contains at least hydrocarbon feed of 1wt% vacuum residuum, the weight based on hydrocarbon feed, and at least the vacuum residuum of 10wt% is converted into the material in boiling below 566 ℃;

(b) hydrocarbon feed of described heating is sent to gas/liquid separation (preferably will arrive from the liquid bottom heat phase of gas/liquid separation the temperature of 593-649 ℃);

(d) will be sent to the first thermal transition district from the described liquid phase that comprises residual oil of at least a portion of described separator and (preferably comprise coke granule, coke granule/fresh feed that preferred described district has a 1:1 at least is than (wt/wt) (preferred 3:1 at least, preferred 5:1 at least, or from 1:1 to 50:1, preferably from 3:1 to 30:1), based on recycle coke solid and the weight that enters the fresh feed in described district), with the described liquid phase that comprises residual oil of thermal transition at least a portion;

(e) liquid phase of described thermal transition is sent to gas/liquid separation, to form the second gas phase and second liquid phase, described separator is connected with the steam cracker furnace fluid;

(f) described the second gas phase is sent to described steam cracker furnace with described the second gas phase of thermal transition at least a portion (or the second gas phase can be used as fuel or blending stock); With

(g) reclaim at least alkene of 30wt% (weight of the total hydrocarbon material based on leaving radiant-type furnace) from the material of the radiant-type furnace that leaves described steam cracker furnace.

Brief Description Of Drawings

In with figure below, similar equipment and/or method steps are determined by same numeral.

Fig. 1 is the schema of an embodiment of the inventive method.

Fig. 2 is the schema of an embodiment of the inventive method.

Fig. 3 is the schema of an embodiment of the inventive method.

Fig. 4 is the schema of an embodiment of the inventive method.

Detailed Description Of The Invention

The present invention relates to comprise heavy feedstocks steam cracker and thermal transition unit (for example, delay coking device, fluid coker, the Flexicoker of the vacuum residuum gas/liquid separation (for example, separating tank) of integration ^tM, viscosity breaking device, shortening viscosity breaking device) comprehensive, wherein vacuum residuum is converted into to the more component that is suitable for steam cracking of lightweight.(" being suitable for steam cracking " refers to material that can cracking in steam cracker).By closely integrating two kinds of conversion processes, total process can be effectively changes into the chemical of high value by the heavy feedstocks of wide region more, makes fouling minimize simultaneously.For the purposes of the present invention, steam cracker furnace (also referred to as " steam cracker ") is the pyrolysis oven with two major sections or stove: convection zone and radiation section, wherein hydrocarbon feed is usingd liquid (except the lightweight material entered as gas) and is entered the convection zone of low harsh stove, and common high-temperature gas heating and the gasified raw material from radiation section by indirect contact wherein, and optionally contact raw material with steam.Subsequently, the raw material of gasification and vapour mixture are sent in radiation section, wherein usually approximately under 10 to about 50psig pressure (69 to 345kPa-gauge pressure) be rapidly heated to harsh hydrocarbon cracking temperature, for example at about 1450 ℉ (788 ℃) to the about scope of 1650 ℉ (900 ℃), with the thorough thermally splitting of the stream of supplying raw materials.The product obtained generally includes alkene, aromatic hydrocarbons and diolefine.

The residual oil that this paper is used refers to the complex mixture of heavy crude compound, otherwise known in the art be Residual oil (residuum) or residue (residual).Nominally long residuum is the bottoms generated in air distillation when the terminal of the heaviest distillage is 650 ℉ (343 ℃), and is called as 650 ℉ ⁺(343 ℃ ⁺) residual oil.Vacuum residuum be when nominally final product of distillation is 1050 ℉ (566 ℃) under reduced pressure from the bottoms of tower, and be called as 1050 ℉ ⁺(566 ℃ ⁺) residual oil.(term " nominally " refer to that rational expert may disagree with for these terms point of contact really here, but may no more than +/-50 ℉ or +/-100 ℉ at most).This 1050 ℉ ⁺(566 ℃ ⁺) partly comprising bituminous matter, it is considered to traditionally for steam cracker is problematic, causes serious fouling and potential corrosion of equipment or erosion.Except as otherwise noted, term used herein " residual oil " refers to 650 ℉ ⁺(343 ℃ ⁺) residual oil and 1050 ℉ ⁺(566 ℃ ⁺) residual oil; Note 650 ℉ ⁺residual oil comprises 1050 ℉ ⁺residual oil.According to the present invention, at least a portion that gasified 650 ℉ ⁺residual oil, until at least 1050 ℉ ⁺boiling point fraction, for example, when when steam is combined, and/or in pressure decreased or the decomposition tank at steam cracker during flash distillation.Term " hydrocarbon feed that comprises vacuum residuum ", " hydrocarbon feed that comprises long residuum ", " hydrocarbon feed that comprises residual oil " etc. refer to the weight based on hydrocarbon feed, there is (preferred 1wt% at least in definite residual oil with 0.1wt% at least, preferred 10wt% at least, preferred 15wt% at least, preferably 20wt% at least).

Term " flash tank ", " flash distillation pot ", " separating tank " were used interchangeably in this article with " separating pot "; They are known in the art, are commonly referred to as the container or the system (" gas/liquid separation ") that go out liquid phase from gas phase separation.Term " flash distillation " is commonly referred to as the material phase transformation to gas phase by liquid phase in the container of realizing at least a portion by reducing pressure and/or increase temperature.The separating tank of integrating is the gas/liquid separation be connected with the steam cracker fluid.Particularly, the convection zone fluid communication of the separating tank of described integration and steam cracker, its Raw is heated (optionally with overheated vapor mixing) and is sent in the described separating tank as the gas/liquid separation operation, thereafter in the future the gas of self-separation tank turns back to described steam cracker, preferably to convection zone or radiation section or the two.Adding of steam can further help flash separation by reducing hydrocarbon partial pressure, helps 750 ℉ ⁺(399 ℃ ⁺) to 1050 ℉ ⁺(566 ℃ ⁺) (preferred even most 1100 ℉ ⁺(593 ℃ ⁺)) conversion and the gasification of residue oil fraction, and prevent fouling.

The integration of preferred flash tank or gas/liquid separating device and they and pyrolysis unit is before at United States Patent(USP) Nos. 7,090,765,7,097,758, and description in 7,138,047, and it is incorporated into herein by reference.For the purposes of the present invention, another kind of effectively as the equipment of flash tank, as " gas/liquid separation ", be described in U.S. Patent No. 6,632, in 351.

Described gas/liquid separation causes that the coking feed material remains under liquid temperature and pressure and operates those parts, preferably approximately at the temperature between 375 to 525 ℃, operating, preferred 400-500 ℃, preferably by 800 ℉ (approximately 425 ℃) and about 870 ℉ (approximately 465 ℃), but usually be no more than approximately 900 ℉ (approximately 482 ℃).

According to the present invention, the crude oil that comprises residual oil or its cut are applied the raw material of steam cracker furnace.The charging of suitable more low value can comprise the more crude oil of heavy usually, and the crude oil of described more heavy is defined as due to high 650 ℉ ⁺(343 ℃ ⁺) residual oil concentration, high-sulfur, high total acid value (TAN), high naphthenic hydrocarbon, high aromatic hydrocarbons, and/or low hydrogen richness those have the hydrocarbon feed of low api gravity as a result.

As used herein crude oil refers to the whole crude produced by well head, production site facility, traffic facilities or other initial fields treatment facility when it, optionally comprise by the step of desalination, processing, and/or other can be necessary so that the crude oil that its distillation of routine for refinery is acceptable step processing.Suppose that as used herein crude oil comprises residual oil.

Crude oil fractions is obtained by the refinery pipe still usually.Although obtaining crude oil fractions any by the refinery pipe still and can be used for the present invention, is still to comprise all or part of original 1050 ℉ that exist in the whole crude obtained by well head by significant advantage provided by the invention ⁺(566 ℃ ⁺) crude oil of residual oil or the charging that crude oil fractions can be used as steam cracker.In one embodiment, the crude oil or other raw material that enter native system can comprise 1050 ℉ at least about 1wt% ⁺(566 ℃ ⁺) residual oil, preferably at least about 1050 ℉ of 5wt% ⁺(566 ℃ ⁺) residual oil, and more preferably at least about 1050 ℉ of 10wt% ⁺(566 ℃ ⁺) residual oil, be up to 1050 ℉ of about 50wt% ⁺(566 ℃ ⁺) residual oil.

Usually residual oil comprises for example naphthenic acid (measure according to TAN according to ASTM D-664, TAN refers to the total acid value meaned with the every gram of milligram (" mg ") KOH (" g ") sample) of metal, sulphur and nitrogen and high molecular (C12+) of a high proportion of undesirable impurity.Still, another advantage of the present invention is that the charging of being rich in one or more these impurity can easily be processed.In some embodiments, the present invention can have 566 ℃ of one or more (preferably two kinds, three kinds, four kinds, five kinds, six kinds or seven kinds) following character ⁺on residual oil, put into practice: 1) based on 566 ℃ ⁺the weight of residual oil, the Ni of 50ppm or more, or 100ppm or more, or 125ppm or more; And/or 2) based on 566 ℃ ⁺the weight of residual oil, 200ppm vanadium or more, or 500ppm or more, or 900ppm or more; And/or 3) based on 566 ℃ ⁺the weight of residual oil, the sulphur of 4wt% or more, or 5wt% or more, or 6wt% or more; And/or 4) at least 0.1 TAN, or at least 0.3, or from approximately 0.1 to approximately 20, approximately 0.3 to approximately 10, or approximately 0.4 to approximately 5; And/or 5) 19 or api gravity still less (ASTM D6822,15.5 ℃); And/or 6) at least 0.04 gram C ₅the C of the every gram residual oil of bituminous matter ₅asphalt content (" C ₅bituminous matter " refer to bituminous matter insoluble in pentane, as measured by ASTM method D2007); And/or 7) kinematic viscosity of 10cSt (as measured by ASTM D445) at least under 37.8 ℃.Can it be 566 ℃ that by crude oil, are obtained at example residual oil used herein ⁺residual oil, described crude oil includes but not limited to the crude oil from following world region: the United States Gulf bank, Southern California, Alaska north slope, Canada's Tar sands, the Transport Model for Alberta area, Gulfian Campeche, Argentina Sheng Haoerhe basin, Brazil Sang Tuosi and Kan Bosi basin, Egyptian the Gulf of Suez, Chad, the Britain North Sea, Angola coastal waters, China Bohai Sea Gulf, the Xinjiang, China Kelamayi, Iraq's Zagros, Kazakhstan the Caspian Sea, the Nigeria coastal waters, the Madagascar northwestward, Oman, Holland Schoonebek, the Su Liya state of Venezuela, the Su Mendala of Malaysia and Indonesia.This paper in addition useful residual oil comprises by US7, the crude oil of describing with " disadvantageous " in 678,264 obtain 566 ⁺℃ ⁺residual oil, be incorporated to this paper by reference.

In preferred embodiments, wherein charging comprises 1050 ℉ that comprise appreciable amount ⁺(566 ℃ ⁺) crude oil or the long residuum of residual oil, for example, 10wt% or more 1050 ℉ ⁺(566 ℃ ⁺) residual oil, or 20wt% or more 1050 ℉ ⁺(566 ℃ ⁺) residual oil, or 30wt% or more 1050 ℉ ⁺(566 ℃ ⁺) residual oil, 40wt% or more 1050 ℉ ⁺(566 ℃ ⁺) residual oil, or even up to 50wt% or more 1050 ℉ ⁺(566 ℃ ⁺) residual oil, make the charging that comprises residual oil at first be sent to the steam cracker furnace with the separating tank of integrating.

Subsequently, make to be sent to thermal transition unit, for example delay coking device, fluid coker, Flexicoker from the bottom material of the first separating tank ^tM, viscosity breaking device, or shortening viscosity breaking device, wherein by bottom material heating and at least the vacuum residuum of 30wt% (weight based on charging) be converted into 1050 ℉ ^-(566 ℃ ^-) fraction.As used herein 1050 ℉ ^-(566 ℃ ^-) fraction is defined as usually 1050 ^f-(566 ℃ ^-) the following hydrocarbon seethed with excitement.The residual oil of thermal transition is incorporated into to separating tank to form top gas phase and phase of the liquid end, and described tank is integrated in steam cracker furnace.Described gas phase is sent to the radiant-type furnace in described steam cracker furnace.At least the alkene of 30wt% reclaims (weight of the total hydrocarbon material based on leaving radiant-type furnace) from the material that leaves radiant-type furnace.Add steam further to help flash separation by reducing hydrocarbon partial pressure, help 750 ℉ ⁺(399 ℃ ⁺) to 1150 ℉ ⁺(621 ℃ ⁺) conversion and the gasification of residue oil fraction, and prevent fouling.

Described fluid coker preferably includes the air gasification device (or partial oxidation reactor) of integration, and it is used to coke is converted into to fuel gas by lower steam/air gasification and burning between about 1400-1800 ℉ (760-982 ℃).Can promote gasification by co-fed oxygen or by the air that uses oxygen enrichment.Will be from the continuous taking-up from gasifier of the coke of the partial gasification of the heat of this gasification reaction, and be fed to one or more solid transmission lines, wherein it for example, contacts with the base material that one or more steam cracker furnace of gas/liquid separation (separating tank) by being equipped with integration reclaim.This irreducible oil cut is converted to the mixture of the more light hydrocarbon that comprises high concentration ethylene and propylene at 1300-1800 ℉ (704-982 ℃).Although the transfer line reactor can arrange in several ways, preferred similar to for fluid catalytic cracking unit be set; For example, transfer line operates as the vertical-lift pipe reactor, the solid of wherein said heat contacts with the charging of the bottom that approaches riser tube, and solid and steam are along upwards transmission of riser tube, and described solid is used the swirler of one or more series connection to separate with steam.Perhaps, transfer line can be used as " downtake " or downflow reactor operation.No matter specifically arrange, for hot coke is contacted with oil residues, the transfer tube reactor is very effective.

Perhaps, the vacuum residuum from refinery (fractionating out) directly can be sent to the residual oil conversion unit and subsequently as the raw material of steam cracker furnace of the separating tank that is equipped with integration from crude oil.

Preferably, flash tank preferably operates to the temperature of about 870 ℉ (approximately 465 ℃) at about 800 ℉ (approximately 425 ℃), but also usually not higher than about 900 ℉ (approximately 482 ℃).650 ℉ have further been promoted by flash tank flash distillation material to obtain top gas and liquid bed material ⁺(343 ℃ ⁺) gasification of residual oil.

Steam cracking provides ethene, propylene, butylene, the C except needs separately ₅alkene and diene, and the mononuclear aromatics product also comprises oil fuel, tar and the SCN (petroleum naphtha of steam cracking) of remarkable productive rate in addition.It is effective especially and favourable that method of the present invention is integrated for steam cracker, because described method has realized the residual oil of significantly higher level, is converted into chemical, non-scaling, and it makes cooling and reheats the demand that the midbody product material flows and minimize.

The product liquid of producing in thermal cracking residue can be in steam cracker the chemical of production high yield and the tendency that shown the fouling steam cracker furnace reduced (to 1050 ℉ ⁺(566 ℃ ⁺) residual oil).

The present invention relates to in one way from the method for heavy feed stock production of chemicals, wherein more vacuum residuum is converted into fuels and chemicals in large quantities.Usually, described method relates to the integration of heavy feedstocks steam cracker and the second thermal conversion reaction device of the vacuum residuum separating tank that comprises integration, and in the second thermal conversion reaction device, vacuum residuum is converted into the lighter component that is suitable for steam cracking.The second thermal conversion reaction device is usually at the time/temp window operation similar with coking process to conventional viscosity breaking, although the condition of the production fuel than common employing a little under the condition of milder operation can be favourable.In one embodiment, in method described herein, 25 ℃ or more (or 50 ℃ or more, or 75 ℃ or more) lower operation below the service temperature of the stove section of the steam cracker of thermal conversion reaction device after the thermal conversion reaction device.In some embodiments, the preferably described not condensation by the radiation section of steam cracker than light liquid and gas of cascade.By closely integrating two kinds of method for transformation, a kind of operation and a kind ofly operate under high severity under relatively mild severity, described method can be converted into wide multiextent heavy feedstocks the chemical of high value.(when stipulating reactor or reaction zone for " operating in " a certain temperature, the material that it refers in reactor or district has been heated to that temperature).

In the following drawings and specification sheets, can be often referred to any gas/liquid separation device with reference to separating tank.

Basic flow sheet of the present invention shows in Fig. 1, wherein hydrocarbon feed (comprising long residuum) 100 introduced to the first thermal conversion reaction devices 600, and wherein at least the residual oil of 30wt% (preferably at least 50%, preferably at least 70%, preferably approximately 90%) is converted into 1050 ℉ ^-(566 ℃ ^-) fraction and/or petroleum coke.Subsequently whole liquids and gases products are introduced to (207) to separating tank 205 (usually in the lower operation of 800-900 ℉ (423 to 482 ℃)), described tank (for example is connected with steam cracker furnace 200 (having convection furnace 206 and radiant-type furnace 250) fluid, be incorporated into steam cracker furnace 200), to form top gas phase 210 and liquid bottom phase 220.Directly or by well heater gas phase 210 is sent to the radiant-type furnace 250 in described steam cracker furnace 200 subsequently, described well heater is for example the convection zone 206 of dispatch tube well heater or steam cracker 200, wherein radiation section operation under 750 to 900 ℃ usually, and at least the radiation section charging of 30wt% (preferably 40% or more) is converted to light olefin (C for example ₂, C ₃, C ₄), described light olefin reclaims (weight of the total hydrocarbon material based on leaving radiant-type furnace) from the material 221 that leaves radiant-type furnace.

Another basic flow sheet of the inventive method shows in Fig. 2, wherein heat packs containing the hydrocarbon feed 100 (usually in the convection furnace 206 of steam cracker furnace) of residual oil and, preferred 10wt% (preferred 20wt% at least at least, preferred 25wt% at least, or from about 20-30%) vacuum residuum is converted into 1050 ℉ ^-(566 ℃ ^-) cut.Whole chargings are heated to about 750-850 ℉ (399-454 ℃).Subsequently the raw material of heating is transmitted to 207 to separating tank 205 (preferably being incorporated in steam cracker furnace), usually in the lower operation of 800-900 ℉ (423-482 ℃).Subsequently the raw material of heating is separated to (gravity settling by centrifugal force and coalescent drop separates in flash tank usually) with the liquid bottom that forms top gas phase 210 and comprise described residual oil mutually 220.Subsequently, liquid bottom 220 is sent to thermal conversion reaction device 300 mutually, optionally comprises coke granule, wherein it is changed into the more molecule 223 of the boiling below 1050 ℉ (566 ℃) of lightweight higher.Subsequently, the molecule of described more lightweight 223 is sent to separating tank 205 ^*(operation under 800-900 ℃ usually), described tank preferably is incorporated in steam cracker furnace, to form the second top gas phase 210 ^*with second liquid bottom phase 220 ^*.Subsequently by top gas phase 210 ^*be sent to the radiant-type furnace 250 in steam cracker furnace ^*(operation under 750-900 ℃ usually), be preferably separating tank 205 ^*the steam cracker furnace of integrating with it.Afterwards, light olefin (for example, the C of 30wt% (preferably at least 40%) at least ₂, C ₃, C ₄alkene) reclaim (weight of the total hydrocarbon material based on leaving radiant-type furnace) in the material that leaves radiant-type furnace 225.

Another basic flow sheet of the inventive method shows in Fig. 3.By heavy feed stock crude oil or vacuum residuum 101 (preferably comprise about 10-50% at vacuum residuum scope (1050 ℉ ⁺(566 ℃ ⁺) in the molecule of boiling) 100 be fed in the first steam cracker furnace 200, described the first steam cracker furnace 200 comprises the separating tank 205 of integration.Whole chargings are heated in the convection zone 206 of stove to about 750-850 ℉ (399-455 ℃).All chargings transmit 207 and enter separating tank tripping device 205, wherein about 1000-1100 ℉ (538-593 ℃) below the molecule of boiling be evaporated (or keep evaporate) and with the compound separation of the more heavy that remains on liquid phase.Material usually enters described tank and evaporates by using steam stripped or extracting promotion with light hydrocarbon at the temperature of about 800-850 ℉ (427-454 ℃).Gas enters the radiation section 250 of the first steam cracker furnace by top 210, yet heavy liquid is taken out from the bottom of separating tank 220.The heavy liquid molecule is joined in the second conversion reactor 300 subsequently, wherein heavy liquid is thermally cracked into the more molecule of lightweight.Subsequently, make lighter molecules enter into and be incorporated into steam cracker furnace (not shown) tank separating device 400 by 221, wherein at the molecule of boiling below about 538-593 ℃, be evaporated (or keep evaporation) and separate from the compound of the more heavy liquid phase still.Material usually enters described tank and evaporates by using steam stripped or extracting promotion with light hydrocarbon at the temperature of about 427-470 ℃.Steam enters the radiation section (not shown) of steam cracker furnace by top by pipeline 410, yet bottom stream is taken out by the bottom of separating tank by pipeline 420.Steam can be incorporated into to (not shown) in steam cracker furnace.Bottom stream 420 from separating tank can be for oil fuel except other.In preferred embodiments, the material that leaves the thermal conversion reaction device can not introduced in the first steam cracker again.

Preferably from the heavy liquid of several stoves that are equipped with separating tank in conjunction with in the second vacuum residuum conversion reactor, to realize better scale economics.The form that the second conversion reactor can directly be combined with steam cracker furnace and can be adopted delay coking device, fluid coker, this coker of Fick (flexicoker), viscosity breaking device, shortening viscosity breaking device or other suitable conversion reactor to design.Optionally, before entering coking reactor, can be by reheating in reboiler or stove or by with high-temperature gas, for example steam or hydrogen contact and further makes feeding preheating to about 800-900 ℉ (427-482 ℃).In the second conversion reactor, a high proportion of vacuum residuum molecule (for example,, approximately more than 50%) is thermally cracked into the molecule of the more lightweight of boiling below 1050 ℉ (566 ℃).The once common by conversion of vacuum residuum molecule is the scope of 30-60% in viscosity breaking, or once by shortening viscosity breaking or coking, reaches 95% or more most.This is by balanced reaction time and the residence time, and in the conversion vessel operated under thermal insulation, the lighter product liquid of extraction is realized.Transform lower or the more hydrogen balance of low hydrogen content charging in order to remain on high-level residual oil, most heavy vacuum residuum molecule is converted into solid coke product or the heavier tarry bottom fraction of transferring to of low hydrogen content.In shortening viscosity breaking device, except producing the heavier tarry bottom fraction of low hydrogen content, add hydrogen with the feed heteroatoms to produce H ₂s, NH ₃and H ₂o, and the alkene fragment that adds to cracking is to prevent coking.In the situation that delay coking device continues reaction until described tank is filled solid coke gradually.Subsequently charging is switched to the second tank, coke is reclaimed from the first tank simultaneously, and continue the method in the mode of circulation.In preferred embodiments, will be fed to the second steam cracker furnace that is incorporated to the integration separating tank from gas and the product liquid of pyrogenic reaction.Compare (or for supplying the stove group of coker feed) with the first stove, this stove can operate under slightly lower separating tank temperature or cut point, preferably the second separating tank 25 ℃ or more (preferably 50 ℃ or more, preferably 75 ℃ or more) lower operation below the service temperature of the first separating tank.The molecule of the more lightweight produced in coking (or second transform) reactor keeps evaporation and is sent to the radiation section of steam cracker, and more the vacuum gas oil of heavy (VGO) molecule and the material that do not transform in coker from the bottom taking-up of the second separating tank.In preferred embodiments, these molecules are disposed by other means, for example sneak into oil fuel, and, as usually put into practice in the fuel coking method, recycle back is not to coker.In another preferred embodiment, can partly use outlet and the quenching of the stream of the distilling material between the separating tank entrance of water cooler VGO or coker from the hot gas at coker top, to promote the further condensation of the heavier VGO component of low hydrogen content.

Although vacuum residuum coking and gas oil steam cracking are well-known methods, coker is unknown with the integration of the steam cracker furnace of the separating tank that comprises integration.In addition, usually preferably make the bottom material be circulated to the obliteration procedure coker to maximize the productive rate of light Fuel component more or fuel feedstocks.The very compound of infusibility is produced in the operation of this bottom cycle, the soluble polynuclear aromatics of heptane for example, and as chemical, charging is inappropriate for it.Unaccommodated especially raw material is the molecule that comprises 4 or how thick aromatic ring.The fuel coker is equipped with large main fractionator usually, its by be mixed for the preheating fresh feed with the coker product and by mixed coking device raw material and coker tank gas streams for cleaning the coker gas of entrained drip.The bottom material reenters reactor with this fresh feed.In the process for steam cracking of integrating, eliminated this main fractionator.

In practice of the present invention, the separating tank of integrating is efficient especially and is effectively and non-scaling for the operation of heavy feedstocks steam cracking and coking method, because it allows easily change consistent with feedstock property of cut point between gas and heavy liquid.

A kind of particularly preferred setting is the direct integration of method for thermal cracking and steam cracker.Directly integrate and refer to that the heating of steam cracker convection zone enters the charging of heat conversion device and the effluent of heat conversion device directly is sent to separating tank, and be sent to subsequently radiation section and by any intermediate heat exchanger.

Preferred thermal conversion reaction device used herein comprises delay coking device, fluid coker, Flexicokers ^tM, viscosity breaking device and shortening viscosity breaking device.

The preferred basic setup of thermal conversion reaction device is similar to delay coking device.Described method particularly: i) for example, slightly than operation under low severity (, from 800-900 ℉ (427-482 ℃), preferred 800-850 ℉ (427-454 ℃)), ii) use the every kg residual oil raw material of about 0.1-1.0kg steam, iii) operate drum under lower appropriate hydrocarbon gas dividing potential drop and/or shorter gas residence time, iv) separate coking gas by the heavy liquid of carrying secretly in the separating tank equipment of integrating, and v) preferably once-through operation and there is no bottom cycle.Delayed coking is " Tutorial:Delayed Coking Fundamentals. " article 29a at P.J.Ellis and C.A.Paul autograph, Topical Conference on Refinery Processing, 1998Great Lakes Carbon Corporation (its can from http:// www.coking.com/DECOKTUT.pdfdownload) in article, describe.In delay coking device, by directly contacting the liquid that makes product gas and carry secretly in the tank as distillation tower, with colder feed heat, exchange.This tank is approaching the lower operation of 50psig (345kPa) usually.This technology causes changing into fully leaves abrogating as the Reusability of the heavy coker liquids of the gas of the tank of distillation tower and the coke assembled in drum.Leave as the bottom heating liquid feeding of the tank of distillation tower and heat exchanger usually at 360-400 ℃.The liquid of this heat is transmitted by a pump, and described pump is promoted to 300-600psig (2.1-4.1MPa) by liquid pressure.The feed flow of heat pressurization is by the coker stove, and described charging therein is heated to and approaches 500 ℃.The stove effluent that approaches 500 ℃ and 60psig (414kPa) flows in drum, and described drum is the separate solid coke from steam and the drop carried secretly.Can remove subsequently volatiles and send it to steam cracker (preferably thering is the steam cracker of integrating separating tank), and stay coke.The material that is sent to steam cracker is converted into alkene subsequently.

In another embodiment, for example, in heating zone (delay coking device), heating, is wherein collected volatile matter and forms coke for example, to coking temperature (being up to 649 ℃) and be sent to subsequently the coking district from the liquid phase of the first gas/liquid separation at top.Preferably, make to stand delayed coking from the liquid phase of the first gas/liquid separation, it relates to gas, liquid material stream and the coke of thermolysis to produce multiple boiling range of petroleum residual oil.In delayed coking method, in the well heater of firing or tube furnace, rapid heating is from the liquid phase of the first gas/liquid separation, to be sent to drum from the liquid phase of the heating of the first gas/liquid separation subsequently, described drum remains on the condition that coking occurs, usually the temperature that is greater than approximately 400 ℃ super-barometric point under.The charging of the heating in drum also forms the volatile constituent (steam cracker that preferably has the separating tank of integration) that is removed and is sent to steam cracker, and coke is stayed.The material that is sent to steam cracker is converted to alkene subsequently.

If use the shortening visbreaking reactor as thermal conversion reaction device 300, the hydrogen-containing gas of mink cell focus and catalyzer (for example metallic sulfide) and molecule (H for example so ₂, synthetic gas, fuel gas) mix, and a high proportion of vacuum residuum molecule, for example, at least about 60%, between even about 60-80%, or even be up to 95% be converted to the lighter molecule seethed with excitement 1050 ℃ (566 ℃) below.Usually operational condition comprises the temperature of 785-900 ℉ (418-482 ℃), the residence time of 2-100 minute (0.1-5LHSV (liquid hourly space velocity)), the hydrogen processing rate of 500-5000SCF/B, and the working pressure of 100-3000psig (0.689-20.7MPa).Preferred condition is about 785-860 ℉ (418-460 ℃), 10-40 minute (0.2-2LHSV), 1000-2500SCF/B, and 500-1500psig (3.45-17.2MPa).Although other design is possible, common reactor design comprises coil reactor, the coil reactor in conjunction with pump around cracking case, or with the slurry state bubbling bed of liquid recirculation.Usually, optimize reactor condition with coupling charging quality; For example, lower quality charging can require more exacting terms to transform with the height of realizing the 50-95% scope, preferred about 60-80%.Use conventional facility (height and light pressure separator) to remove gas and product liquid and the untapped hydrogen that circulates to the method after reactor.The catalyzer used in the shortening viscosity breaking method is usually based on the sulfide transition metal.The most common metal is Mo, Ni and Co.When the method operates with slurry, catalyzer is usually based on being dispersed in carbonaceous main body (a.k.a Microcat

) micron or the metal sulfide grain of submicron-scale.Described Microcat can be based on moly-sulfide; Those that other transient metal sulfide is for example produced by tungsten, vanadium, iron, nickel and cobalt; Or the moly-sulfide of being combined with one or more these selectable transient metal sulfide, or the combination of selectable transient metal sulfide.Although molybdenum provides gratifying operation for many chargings separately, the use of other metal or multimetallic catalyst system can provide improved performance to conversion, hydrogen addition and the desulfurization of residual oil, for example higher catalytic activity.Fresh catalyzer is usually by by heavy VGO cut and low-cost catalyst precursor, and for example ammonium molybdate or phospho-molybdic acid mix and are heated to 600-800 ℉ (316-427 ℃) and form in 10-60 minute.The pre-formed of catalyzer preferably carried out under hydrogen and H2S or elementary sulfur existence.The Microcat produced in this mode

many conversions, filter and re-use circulation in be stable.Yet catalyzer can deactivate within the long time.Due to this reason, it can be favourable removing little removing material stream from method.This " with what cross " catalyzer can be regenerated or again form fresh catalyst precursor in independent equipment., adopt and be generally used for fixed bed residuum hydrodesulfurization (by the charging that comprises 650+ residual oil, producing low sulphur fuel oil), FCC feed pretreatment during in fixed bed operation when method, and the conventional fixed bed catalyst of heavy feedstocks hydrocracker.

In generation nineteen sixty, Exxon has developed the Flexicoking that this paper can use ^tMmethod and describing in detail in the formerly patent of wide region and the textbook about the residual oil processing technology.For example, U.S. Patent No. 3,671,424, be incorporated to this paper by introducing, and described examples suitable fluid coking equipment and method is for the purposes of this paper.

In another embodiment, the liquid phase of leaving the first gas/liquid separation further is heated to for example 1000-1200 ℉ (538-649 ℃), preferred 1100-1200 ℉ (593-649 ℃), the temperature of preferred about 1125-1190 ℉ (607-643 ℃), usually in the low coil pipe of the convection zone of steam cracker, carry out, wherein usually normally viscosity breaking of the material of part heating, then make water (for example steam) quenching and evaporate the material of viscosity breaking.Subsequently the viscosity breaking material of evaporation is sent to the second gas/liquid separation, wherein the material of viscosity breaking is separated into second liquid phase and the second gas phase.The second gas phase be introduced into subsequently steam cracker (in convection zone or radiation section or the two) and from the material that leaves radiant-type furnace, reclaim at least the alkene of 30wt% (preferably 40% or follow many, preferred 50wt% or more) (weight of the total hydrocarbon material based on leaving radiant-type furnace).

Usually, reaction kinetics and reaction heat calculate and show when residual oil is exposed to 1200 ℉ (649 ℃) 2 seconds roughly, and the viscosity breaking obtained almost completely transforms.But, because viscosity breaking is thermo-negative reaction, it is inadequate only quickly heating up to 1200 ℉ (649 ℃).In viscosity breaking subsequently, residual oil is cooled to 950 ℉ that occur roughly 60% ⁺(510 ℃ ⁺) to 950 ℉ ^-(510 ℃ ^-) degree that transforms.Higher temperature has increased the transformation efficiency of viscosity breaking, but the second pyrogenic reaction also occurs.Therefore, in preferred embodiments, in lower convection zone rapid heating from the bottom stream of the first separating tank to 1000-1200 ℉ (538-649 ℃) (preferred 1100-1200 ℉ (593-649 ℃), preferred about 1200 ℉ (649 ℃)), wherein the continuous replacement of flue gas heat the heat absorption loss.In order to be minimized in the fouling in convection zone, bottom stream is only heated so that high-speed residual oil is washed coke precursors off continuously from internal surface in one way.If some coking occur really, periodically the steam/air decoking is by calcination/it is peeled off from pipe.

In selectable embodiment, convection tubes can be by the solid outer tube around porous sintered metal, wherein steam is in anchor ring.Vapor pressure is higher than causing that thereby the operation pressure that steam oozes out the sintering inner tube prevents sedimentation of coke.

Subsequently, when leaving convection zone, (for example, 1000-1200 ℉ (538-649 ℃)) fast quench is expected in the bottom of viscosity breaking, otherwise the extra residence time can be caused excessive coking.Steam and/or water are excellent quenching mediums, because they make a large amount of newly-generated light fractions evaporations reduce hydrocarbon partial pressure.Note, in this quench operation, have sufficient liquid, it prevents coking.In gas phase, bimolecular pyrogenic reaction is not dominant (comparing with liquid phase), because hydrocarbon concentration is low.In preferred embodiments, any fouling that still can occur in gas phase is avoided to～840 ℉ (449 ℃) by quenching.In optional embodiment, come a part of bottom stream of autonomous separating tank can contribute to quench operation.

In another embodiment, the second little separating tank separates the light hydrocarbon of viscosity breaking from remaining residual oil.As the first separating tank, engage remaining liquid to the pipeline of the second tank, it separates with appropriate hydrocarbon gas/vapour mixture subsequently in described tank.By at～840 ℉ (449 ℃), operating described the second tank, the fouling in gas phase will be very low.Therefore, gas can be sent to the overhead line of the first separating tank or the first tank.Perhaps, the gas/liquid from quenching can be added to the pipeline of the first separating tank upstream, eliminate the needs to the second separating tank.In addition, two separating tank designs allow the only once viscosity breaking intensely of bottom stream from the first separating tank, have reduced the possibility of serious coking.Note, the second separating tank temperature so not high (hydrocarbon partial pressure is so not low yet) so that bottom stream can not flow and/or can not flow out.

Steam tracing further reduces the gas phase fouling usually.The coking test shows that the superheated coke(oven)gas minimizes the fouling in swirler to arriving 1250 ℉ (677 ℃), and supposition is by preventing liquid deposition master coking mechanism.Therefore, a preferred embodiment of the present invention is to make all containers of gas/liquid separate downstream and pipeline steam tracing prevent liquid deposition by the steam with overheated.Institute's rheme hot steam (it is remarkable hotter than process gas), if these pipelines are heat insulation, eliminated the cold spot that may exist so.Even hotter steam can be for superheated gas to limited extent.If necessary, some tracing steams can be injected directly in gas to provide further overheated.

The high usability of a significant advantage heavy feedstocks of the present invention, and there is no undue coking.

Another basic flow sheet for the inventive method shows in Fig. 4.By heavy feed stock crude oil or residual oil 101 (preferably comprise about 10%-50% at vacuum residuum scope (1050 ℉ ⁺(566 ℃ ⁺)) boiling molecule) be fed in the first steam cracker furnace 200, described the first steam cracker furnace 200 comprises the separating tank 205 of integration.Convection zone 206 at described stove is heated to about 800-900 ℉ (427-482 ℃) by whole charging.Whole preheated feed are led to 207 separating tank separating devices 205, the molecule of wherein evaporation (or keeping evaporation) boiling below about 1000-1100 ℉ (538-593 ℃), and from the heavier still compound separation liquid phase.Material usually enters described tank and evaporates by using steam stripped or extracting promotion with light hydrocarbon in the temperature of about 800-850 ℉ (427-454 ℃).Gas enters the radiation section 250 of the first steam cracker furnace by 210, and heavy liquid is taken out by the bottom of separating tank 220.Subsequently, the heavy liquid molecule is added to the convection zone 206 (or by mix with fresh feed or by being sent to the heating plate area under control of separating) of stove, wherein heavy liquid is become lighter molecule by viscosity breaking.Water or steam 227 are introduced to evaporate lighter molecule (usually outside convection zone).Make subsequently the lighter molecules of viscosity breaking pass through 221 to separating tank separating device 400, described separating tank separating device 400 is incorporated into (not shown) in steam cracker furnace and wherein evaporates (or keeping evaporation) molecule in boiling below about 538-593 ℃, and from still separating in the heavier compound liquid phase.Steam is entered to the radiation section (not shown) of steam cracker furnace by 410, and the bottom material takes out by pipeline 420 from the bottom of separating tank.Steam can be incorporated into to the steam cracker furnace (not shown).Bottom material 420 from separating tank can be for oil fuel except other.In preferred embodiments, the material that leaves the thermal conversion reaction device is not reintroduced in the first cracking device.

In preferred embodiments, the residue vacuum residuum that main conversion and after separating retain in separating tank does not reclaim additionally to be converted into chemical.This remaining material comprises the very compound of infusibility, the insoluble polynuclear aromatics of heptane for example, and it is not preferred for the chemical charging.These remaining molecules transform to produce fuel and obtain better utilised by it being sneaked in oil fuel or optional refinery's residual oil conversion system separating.

In another preferred embodiment, the vacuum resid feed transformed in the present invention comprises the hydrogen higher than 10.0wt%, preferably higher than 11.0wt%.

In another preferred embodiment, the charging that enters thermal conversion reaction device (for example coker or delay coking device) comprises the hydrogen higher than 10.0wt%, preferably higher than 11.0wt%, and preferably higher than 11.5wt%, the weight based on charging.

In another embodiment, the temperature of leaving the gas of thermal conversion reaction device (for example coker or delay coking device) is 750-900 ℉ (399-482 ℃), preferred 780-860 ℉ (416-460 ℃), preferably 800-850 ℉ (427-454 ℃).In another embodiment, the pressure in the thermal conversion reaction device is 30psig (207kPa) the most nearly, preferably reaches most 25psig (172kPa), preferably from 1-20psig (138kPa).

In preferred embodiments, when the convection zone by the first steam cracker furnace leads to the first separating tank of integration, uncolled hydrocarbon feed.The temperature of the uncolled mixture flow that refers to the preferred feedstock liquids and gases reduces and is no more than 30 ℃ (or be no more than 50 ℃, or be no more than 100 ℃).In another embodiment similarly, when the convection zone by the second steam cracker furnace leads to the second separating tank of integration, uncolled hydrocarbon feed.

In another embodiment of method described herein, before entering into the separating tank of integration, thermal transition material (for example residual oil or liquid bottom phase) is sent to the convection zone of steam cracker.

In another embodiment, by molecular hydrogen (gas that usually contains molecular hydrogen), in method, any point joins in the raw material of heating.

In another embodiment, can add in the raw material of heating by any steam of naming a person for a particular job in method.This is particularly useful for helping the evaporation in the separation tank field of integrating.

In particularly preferred embodiments, the thermal conversion reaction device is 649 ℃ or more lowly operation, preferably 640 ℃ or lower, preferably 630 ℃ or lower.

In an especially preferred embodiment, the thermal conversion reaction device is (for example to hang down severe condition, be less than temperature and 30kPa or the lower pressure of 860 ℉ (460 ℃)) the lower delay coking device operated, and the output of self-dalay coker in the future directly is sent to the separating tank (before being sent to the separating tank of integration, the output of self-dalay coker is through the convection zone of steam cracker in the future) be incorporated on steam cracker.In this scheme, the charging that enters delay coking device is heated and is directly flowed in separating pot from the effluent of delay coking device tank in the convection zone of steam cracker, described separations pot and the integration of steam cracker radiation section.Given drum can integratedly be fed to one or more steam cracker furnace that are equipped with the separating tank of integration with supply.A plurality of drums with one or more stoves are also possible with the integration that separates pot.Replace a tank, two or three tank parallel connections can be arranged.Tank can be on steam, and other emptied coke.

In particularly preferred embodiments, vacuum residuum is passed in the steam cracking convection zone, (wherein gas/liquid separation is connected with the steam cracker fluid to be sent to subsequently gas/liquid separation, with the convection zone fluid of steam cracker, be connected especially), thereafter residual oil is changed into to gas phase and liquid phase.Gas phase is sent to identical or different steam cracker, at radiation section or convection zone, or the two.Liquid phase is sent to the thermal transition district, and for example coker, delay coking device, this coker of Fick, catalysis viscosity breaking device or shortening viscosity breaking device, wherein convert it into gas or liquid stream and coke.(wherein gas/liquid separation is connected with the steam cracker fluid with being sent to afterwards gas/liquid separation subsequently gas or liquid stream to be transmitted to convection zone into steam cracker (steam cracker that preferably is different from the first steam cracker), particularly the convection zone fluid of steam cracker is connected), afterwards the gas of heating or liquid stream are converted into to gas phase and liquid phase, with described gas phase is sent in identical or different steam cracker, at radiation or convection zone, or the two.

In another embodiment, the present invention relates to:

1. the method for the hydrocarbon feed that comprises vacuum residuum for cracking comprises:

(a) hydrocarbon feed that will comprise vacuum residuum is sent to the first thermal transition district, wherein by described heating raw materials to be less than 649 ℃ temperature (for example, be less than operation under 649 ℃), wherein at least the vacuum residuum of 30wt% (at least 50wt%, at least 70wt% or at least 90wt%) is converted into the material in boiling below 566 ℃;

(b) residual oil of described thermal transition is incorporated into to gas/liquid separation, to form gas phase and liquid phase, described separator is connected with the steam cracker furnace fluid;

(c) described gas phase is sent to described steam cracker furnace; With

(d) from the salvage material of the radiant-type furnace that the leaves steam cracker furnace alkene of 30wt% (weight of the total hydrocarbon material based on leaving radiant-type furnace) at least.

2. the method for paragraph 1, for example, wherein from the liquid bottom phase of the gas/liquid separation of step (b): be brought to the liquid bottom phase of the temperature (or, be less than 649 ℃) of (, heating or cooling) 538-649 ℃ with viscosity breaking at least a portion; By the liquid bottom phase quenching of viscosity breaking and be sent to subsequently the second gas/liquid separation, wherein viscosity breaking liquid bottom is separated into second liquid phase and the second gas phase mutually afterwards; Second gas phase then be incorporated into to the steam cracker furnace of step (c) thereafter.

3. the method for the hydrocarbon feed that comprises vacuum residuum for cracking comprises:

(a) heat packs is containing the hydrocarbon feed of vacuum residuum with transform at least vacuum residuum of 10wt% and become the material seethed with excitement below 566 ℃;

(b) hydrocarbon feed of described heating is sent to gas/liquid separation;

(d) at least a portion is sent to the first thermal transition district from the described liquid phase containing residual oil of described separator;

(e) liquid phase of described thermal transition is sent to gas/liquid separation to form the second gas phase and second liquid phase, described separator is connected with the steam cracker furnace fluid;

(f) described the second gas phase is sent to described steam cracker furnace with described the second gas phase of thermal transition (at least a portion); With

(g) from the salvage material of the radiant-type furnace that the leaves described steam cracker furnace alkene of 30wt% (weight of the total hydrocarbon material based on leaving radiant-type furnace) at least.

4. the method for paragraph 3, wherein will be heated to from the liquid phase of step (c) temperature of 538-649 ℃ with viscosity breaking at least a portion liquid phase; Afterwards the liquid phase quenching of viscosity breaking also is sent to another gas/liquid separation subsequently, wherein viscosity breaking liquid phase is separated into the liquid phase of viscosity breaking and the gas phase of viscosity breaking; The gas phase of viscosity breaking be incorporated into to the thermal transition district of step (d) thereafter.

5. the either method of paragraph 1-4, wherein will be heated to the temperature of 593-649 ℃ from the liquid bottom phase in the claim 1 of the gas/liquid separation in step in claim 1 (b) or from the liquid phase of step in claim 2 (c).

6. the either method of paragraph 1-5, wherein the thermal transition district comprises coke granule, wherein said district has at least the coke granule of 1:1/fresh feed ratio (wt/wt) (preferred 3:1 at least, preferred 5:1 at least, or from 1:1 to 50:1, preferably from 3:1 to 30:1), based on recycle coke solid and the weight that enters the fresh feed in described district.

7. the either method of paragraph 1-5, wherein said thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, viscosity breaking device or shortening viscosity breaking device.

8. the either method of paragraph 1-5, wherein said thermal transition district is delay coking device.

9. the either method of paragraph 1-8,25 ℃ or how lower operation below the service temperature of wherein said thermal transition district stove section of steam cracker after the thermal transition district.

10. the either method of paragraph 1-9, wherein vacuum resid feed comprises the hydrogen higher than 10.0wt%.

11. the either method of above claim, the charging that wherein enters the thermal transition district comprises the hydrogen higher than 11.0wt%.

12. any means of paragraph 1-11, the temperature of wherein leaving the gas in thermal transition district is 399-482 ℃.

13. the either method of paragraph 1-12, wherein, before entering gas/liquid separation, be sent to the thermal transition residual oil of claim 1 convection zone of steam cracker.

14. the either method of paragraph 2-13, wherein, before entering into gas/liquid separation, be sent to the thermal transition liquid phase of claim 2 convection zone of steam cracker.

15. the either method of paragraph 1-14, wherein the arbitrfary point in described method joins hydrogen or steam the raw material of heating.

16. the either method of paragraph 1-15, wherein said steam cracker convection zone is heated to the charging in thermal transition district, and the effluent in thermal transition district directly is sent to gas/liquid separation, and is sent to subsequently the radiation section of steam cracker, and do not transmit by any intermediate heat exchanger.

17. the either method of paragraph 1-16, the wherein salvage material (weight of total hydrocarbon material based on leave radiant-type furnace) of the alkene of 40wt% from leaving radiant-type furnace at least.

18. the either method of paragraph 1-17, wherein the first thermal transition district is fluid coker.

19. the either method of paragraph 1-18, wherein the first thermal transition district is shortening viscosity breaking device.

20. the either method of paragraph 1-19, wherein the first thermal transition district is to being less than the hydrogenation viscosity breaking device operated at the temperature of 649 ℃ 400.

21. the system of the hydrocarbon feed that comprises vacuum residuum for cracking comprises:

A) be less than the first thermal transition district operated at the temperature of 649 ℃, it is selected from: delay coking device, fluid coker, Flexicoker ^tM, viscosity breaking device or shortening viscosity breaking device, described the first thermal transition district and b) the steam cracker furnace fluid is connected, described b) steam cracker furnace has the gas/liquid separation be connected with described stove fluid.

22. the system of paragraph 21, further comprise the second gas/liquid separation be connected with described thermal transition district fluid.

23. the system of paragraph 21 or 22, wherein the first thermal transition district is fluid coker, and described fluid coker comprises:

I) fluidized-bed gasifier,

Ii) transfer line reactor, it comprises the hydrocarbon opening for feed be connected than the lower part fluid with described separator, and the pyrolysis product outlet line,

Iii) solid pipeline, it is connected with described transfer line reactor than lower part described fluidized-bed gasifier, and

Iv) at least one cyclonic separator, it has the entrance that is connected to described pyrolysis product outlet line, the crackate outlet at described cyclonic separator top, and the solid outlet bottom described cyclonic separator.

24. the system of paragraph 23, further be included in the air/steam entrance of described fluidized-bed gasifier bottom.

25. the system of paragraph 23 or 24, wherein said fluid coker further comprises fluidized-bed well heater container, it has the described well heater container of connection than the recirculated solids pipeline of lower part and described gasifier, with at least one gas pipeline, described gas pipeline the higher part of described gasifier divide and described well heater container than lower part between connect.

26. arbitrary system of paragraph 23-25, wherein said cyclonic separator solid outlet be connected to described fluidized-bed gasifier or described well heater container any one or the two.

27. arbitrary system of paragraph 23-26, comprise that the described heating container of connection and described gasifier are than two solid pipelines of lower part.

28. arbitrary system of paragraph 23-27, wherein said transfer line reactor is the vertical-lift pipe reactor, wherein said solid pipeline and described hydrocarbon feed entrance be connected to described reactor than lower part.

29. arbitrary system of paragraph 23-28, wherein said transfer line reactor is downflow reactors, and the higher part that wherein said solid pipeline and described hydrocarbon feed entrance are connected to described reactor is divided.

In another embodiment, the present invention relates to:

1A. the method for the hydrocarbon feed that comprises vacuum residuum for cracking comprises:

(a) hydrocarbon feed that will comprise vacuum residuum is sent to the first thermal transition district, wherein by described heating raw materials to the temperature that is less than 649 ℃, wherein at least the vacuum residuum of 30wt% is converted into the material in boiling below 566 ℃;

(b) residual oil of described thermal transition is incorporated into to gas/liquid separation to form gas phase and liquid phase, described separator is connected with the steam cracker furnace fluid;

(c) described gas phase is sent to described steam cracker furnace (the preferably radiant-type furnace in steam cracker furnace); With

2A. the method for paragraph 1A, wherein from the liquid bottom phase of the gas/liquid separation of step (b): be brought to the temperature of 538-649 ℃ with the liquid bottom phase of viscosity breaking at least a portion; By the liquid bottom phase quenching of viscosity breaking and be sent to subsequently the second gas/liquid separation, wherein viscosity breaking liquid bottom is separated into second liquid phase and the second gas phase mutually afterwards; Second gas phase then be incorporated into to the steam cracker furnace of step (c) thereafter.

3A. the method for paragraph 1A, wherein the liquid bottom from the gas/liquid separation of step (b) is heated to the temperature of 593-649 ℃ mutually.

4A. the method for paragraph 1A, wherein the thermal transition district comprises coke granule, and wherein said district has at least coke granule of 1:1/fresh feed ratio (wt/wt), based on recycle coke solid and the weight that enters the fresh feed in described district.

5A. the method for paragraph 1A, wherein said thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, viscosity breaking device or shortening viscosity breaking device.

6A. the method for paragraph 5A, wherein said thermal transition district is delay coking device.

7A. the method for paragraph 1A, 25 ℃ or how lower operation below the service temperature of wherein said thermal transition district stove section of steam cracker after the thermal transition district.

8A. the method for paragraph 1A, wherein vacuum resid feed comprises the hydrogen higher than 10.0wt%.

9A. the method for paragraph 1A, the charging that wherein enters the thermal transition district comprises the hydrogen higher than 11.0wt%.

10A. the method for paragraph 1A, the temperature of wherein leaving the gas in thermal transition district is 399-482 ℃.

11A. the method for paragraph 1A, wherein, before entering gas/liquid separation, be sent to the thermal transition residual oil of claim 1 convection zone of steam cracker.

12A. the method for paragraph 1A, wherein the arbitrfary point in described method joins hydrogen or steam the raw material of heating.

13A. the method for paragraph 1A, wherein said steam cracker convection zone is heated to the charging in thermal transition district, and the effluent in thermal transition district directly is sent to gas/liquid separation, and is sent to subsequently the radiation section of steam cracker, and do not transmit by any intermediate heat exchanger.

14A. the method for paragraph 1A, the wherein salvage material (weight of total hydrocarbon material based on leave radiant-type furnace) of the alkene of 40wt% from leaving radiant-type furnace at least.

15A. the method for paragraph 1A, wherein the first thermal transition district is fluid coker.

16A. the method for paragraph 1A, wherein the first thermal transition district is shortening viscosity breaking device.

17A. the method for paragraph 1A, wherein the first thermal transition district is to being less than the hydrogenation viscosity breaking device operated at the temperature of 649 ℃ 400.

18A. the method for the hydrocarbon feed that comprises vacuum residuum for cracking comprises:

(a) heat packs contains at least hydrocarbon feed of the vacuum residuum of 1wt%, the weight based on hydrocarbon feed, and at least the vacuum residuum of 10wt% is converted into the material in boiling below 566 ℃;

(b) hydrocarbon feed of described heating is sent to gas/liquid separation;

(d) at least a portion is sent to the first thermal transition district from the described liquid phase containing residual oil of described separator; With the described liquid phase containing residual oil of thermal transition at least a portion;

(e) liquid phase of described thermal transition is sent to gas/liquid separation, described separator is connected with the steam cracker furnace fluid, to form the second gas phase and second liquid phase;

(f) described the second gas phase is sent to described steam cracker furnace with described the second gas phase of thermal transition at least a portion; With

19A. the method for paragraph 18A, wherein will be heated to from the liquid phase of step (c) temperature of 538-649 ℃ with viscosity breaking at least a portion liquid phase; Afterwards the liquid phase quenching of viscosity breaking also is sent to another gas/liquid separation subsequently, wherein viscosity breaking liquid phase is separated into the liquid phase of viscosity breaking and the gas phase of viscosity breaking; The gas phase of viscosity breaking be incorporated into to the thermal transition district of step (d) thereafter.

20A. the method for paragraph 18A, will be heated to the temperature of 593-649 ℃ from the liquid bottom phase in the claim 1 of the gas/liquid separation in step in claim 1 (b) or from the liquid phase of step in claim 2 (c).

21A. the method for paragraph 18A, wherein the thermal transition district comprises coke granule and described district has at least coke granule of 1:1/fresh feed ratio (wt/wt), based on the recycle coke solid with enter the weight of the fresh feed in described district.

22A. the method for paragraph 18A, wherein said thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, viscosity breaking device or shortening viscosity breaking device.

23A. the method for paragraph 18A, wherein said thermal transition district is delay coking device.

24A. the method for paragraph 18A, 25 ℃ or how lower operation below the service temperature of wherein said thermal transition district stove section of steam cracker after the thermal transition district.

25A. the method for paragraph 18A, wherein vacuum resid feed comprises the hydrogen higher than 10.0wt%.

26A. the method for paragraph 18A, the charging that wherein enters the thermal transition district comprises the hydrogen higher than 11.0wt%.

27A. the method for paragraph 18A, the temperature of wherein leaving the gas in thermal transition district is 399-482 ℃.

28A. the method for paragraph 18A, wherein, before entering gas/liquid separation, be sent to the thermal transition residual oil of claim 1 convection zone of steam cracker.

29A. the method for paragraph 18A, wherein, before entering into gas/liquid separation, be sent to the thermal transition liquid phase of claim 2 convection zone of steam cracker.

30A. the method for paragraph 18A, wherein the arbitrfary point in described method joins hydrogen or steam the raw material of heating.

31A. the method for paragraph 18A, wherein said steam cracker convection zone is heated to the charging in thermal transition district, and the effluent in thermal transition district directly is sent to gas/liquid separation, and is sent to subsequently the radiation section of steam cracker, and do not transmit by any intermediate heat exchanger.

32A. the method for paragraph 18A, the wherein salvage material (weight of total hydrocarbon material based on leave radiant-type furnace) of the alkene of 40wt% from leaving radiant-type furnace at least.

33A. the method for paragraph 18A, wherein the first thermal transition district is fluid coker.

34A. the method for paragraph 18A, wherein the first thermal transition district is shortening viscosity breaking device.

35A. the method for paragraph 18A, wherein the first thermal transition district is to being less than the hydrogenation viscosity breaking device operated at the temperature of 649 ℃ 400.

36A. the system of the hydrocarbon feed that comprises vacuum residuum for cracking comprises:

37A. the system of paragraph 36A, further comprise the second gas/liquid separation be connected with described thermal transition district fluid.

38A. the system of paragraph 36A, wherein the first thermal transition district is fluid coker, and described fluid coker comprises:

I) fluidized-bed gasifier,

Ii) transfer line reactor, comprise the hydrocarbon opening for feed be connected than the lower part fluid with described separator, and the pyrolysis product outlet line,

39A. the system of paragraph 38A, further be included in the air/steam entrance of described fluidized-bed gasifier bottom.

40A. the system of paragraph 38A, wherein said fluid coker further comprises fluidized-bed well heater container, it has the described well heater container of connection than the recirculated solids pipeline of lower part and described gasifier, with at least one gas pipeline, described gas pipeline the higher part of described gasifier divide and described well heater container than lower part between connect.

41A. the system of paragraph 38A, wherein said cyclonic separator solid outlet be connected to described fluidized-bed gasifier or described well heater container any one or the two.

42A. the system of paragraph 38A, comprise that the described heating container of connection and described gasifier are than two solid pipelines of lower part.

43A. the system of paragraph 38A, wherein said transfer line reactor is the vertical-lift pipe reactor, wherein said solid pipeline and described hydrocarbon feed entrance be connected to described reactor than lower part.

44A. the system of paragraph 38A, wherein said transfer line reactor is downflow reactors, and the higher part that wherein said solid pipeline and described hydrocarbon feed entrance are connected to described reactor is divided.

Embodiment

By a series of coking conditions of summing up in ephemeris 1 with three kinds of vacuum residuum of various quality and hydrogen richness.In order to maximize 1050 ℉ that produce with the light gas reduced ^-the cut product liquid, select than usually putting into practice the coking condition of milder on severity.Analysis to determine the productive rate of petroleum naphtha, overhead product and gas oil, and is determined basic liquid product quality (proportion, hydrogen richness etc.) from the product of pyrogenic reaction.

Subsequently, use the realistic model of steam cracking process to estimate the productive rate of the chemical product that can be produced by complete boiling range coking product.The steam cracking products collection efficiency of selecting is outstanding in table 2.That can easily find out that this coking adds that the steam cracking process makes it possible to high yield produces chemical products by vacuum residuum, comprises ethylene/propene and butylene.When initial vacuum residuum has in 11-12wt% or more multiextent higher level of hydrogen, be conducive to the high olefin productive rate.The productive rate of the tar of heavy lesser value and gas oil product reduces and increases along with feed hydrogen content.

Table 1: the coking of the gentleness sternness degree of various quality vacuum residuum

Initial vacuum resid feed	A	B	C
				API ^*	5.4	9.8	16.5
%H	10.18	11.21	12.16
				Condition	?	?	?
Cell pressure psig (kPa)	3(20.7)	20(137.9)	20(137.9)
				The flat equal temperature ℉ of coking bed (℃)	820(438)	800(427)	824(440)
Productive rate wt%	?	?	?
				H ₂S	0.58	0.68	0.20
Methane	2.10	2.08	1.77
				Other C4 ^-	4.10	4.90	5.20

[0212]?

Petroleum naphtha (C5-, 400 ℉ (204 ℃))	11.61	15.75	18.83
				Overhead product (400 ℉-650 ℉ (204-343 ℃))	19.67	21.53	23.69
Bottom material (650 ℉ ⁺(343℃))	38.38	24.38	17.41
				Coke	23.57	24.38	17.41
Hydrogen richness	?	?	?
				Petroleum naphtha (400 ℉ ^-(204℃ ^-))	13.7	14.1	14.2
Overhead product (400 ℉-650 ℉ (204-343 ℃))	12.5	12.64	13.2
				Bottom material (650 ℉ ⁺(343℃))	11	11.8	12.3

^*aPI=American Petroleum Institute (API) is with the proportion of degree

Table 2: the steam cracking productive rate that uses the wide fraction coking liquid of steam cracker process simulation model estimation

Initial vacuum resid feed	A	B	C
				API	5.4	9.8	16.5
SC productive rate wt%	?	?	?
				The productive rate of ethene+propylene+C4	28.4	33.9	38.6
Tar (C17+)	26.7	18.0	13.9
				?	?	?	?

Unless otherwise indicated, the implication of term used herein should adopt the common implication in their this areas; Especially can be with reference to Handbook of Petroleum Refining Processes, the third edition, Robert A.Meyers, editor, McGraw-Hill (2004).In addition, the document that all preference files, patent, patent application, test procedure (for example ASTM method) and other this paper quote is by reference to being incorporated to this paper fully, to this degree, these disclosures are consistent with the present invention and, in all jurisdictions, this being incorporated to allows.In addition, when numerical lower limits and numerical upper limits, when this paper lists, any lower limit is expected to the scope of any upper limit.

Above the present invention describes with reference to numerous embodiments and specific embodiment.Those skilled in the art will propose a lot of variants according to above detailed description.All these obvious variants are in the scope of whole expections of appending claims.

Claims

(c) described gas phase is sent to described steam cracker furnace; With

2. the process of claim 1 wherein liquid bottom phase from the gas/liquid separation of step (b): be brought to the temperature of 538-649 ℃ with the liquid bottom phase of viscosity breaking at least a portion; By the liquid bottom phase quenching of viscosity breaking be sent to subsequently the second gas/liquid separation, wherein the liquid bottom of viscosity breaking is separated into second liquid phase and the second gas phase mutually afterwards; Second gas phase then be incorporated into to the steam cracker furnace of step (c) thereafter.

3. the process of claim 1 wherein that the thermal transition district comprises coke granule, described district has at least coke granule of 1:1/fresh feed ratio (wt/wt), based on recycle coke solid and the weight that enters the fresh feed in described district.

4. the process of claim 1 wherein that described thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, viscosity breaking device or shortening viscosity breaking device.

5. the process of claim 1 wherein 25 ℃ or how lower operation below the service temperature of described thermal transition district stove section of steam cracker after the thermal conversion reaction device.

6. the process of claim 1 wherein that the charging that enters the thermal transition district comprises the hydrogen higher than 11.0wt%.

7. the process of claim 1 wherein and the thermal transition residual oil of claim 1 was sent to the convection zone of steam cracker before entering gas/liquid separation.

8. the process of claim 1 wherein that the arbitrfary point in described method joins hydrogen or steam the raw material of heating.

9. the method for claim 1, wherein the steam cracker convection zone heats the charging in this thermal transition district and the effluent of thermal conversion reaction device directly is sent to gas/liquid separation, and be sent to subsequently the radiation section of steam cracker, and do not transmit by any intermediate heat exchanger.

10. the process of claim 1 wherein that the first thermal transition district is fluid coker.

11. the method for the hydrocarbon feed that comprises vacuum residuum for cracking comprises:

(b) hydrocarbon feed of described heating is sent to gas/liquid separation;

(d) at least a portion is sent to the first thermal transition district with the described liquid phase containing residual oil of thermal transition at least a portion from the described liquid phase containing residual oil of described separator;

12. the method for claim 11, wherein will be heated to from the liquid phase of step (c) temperature of 538-649 ℃ with viscosity breaking at least a portion liquid phase; Afterwards the liquid phase quenching of viscosity breaking also is sent to another gas/liquid separation subsequently, wherein viscosity breaking liquid phase is separated into the liquid phase of viscosity breaking and the gas phase of viscosity breaking; The gas phase of viscosity breaking be incorporated into to the thermal transition district of step (d) thereafter.

13. the method for claim 11, wherein the thermal transition district comprises coke granule and described district has at least coke granule of 1:1/fresh feed ratio (wt/wt), based on the recycle coke solid with enter the weight of the fresh feed in described district.

14. the method for claim 11, wherein said thermal transition district is delay coking device, fluid coker, Flexicoker ^tM, viscosity breaking device or shortening viscosity breaking device.

15. the method for claim 11, wherein said thermal transition district is delay coking device.

16. the method for claim 11, the charging that wherein enters the thermal transition district comprises the hydrogen higher than 11.0wt%.

17. the method for claim 11, wherein, before entering gas/liquid separation, be sent to the thermal transition residual oil of claim 1 convection zone of steam cracker.

18. the method for claim 11, wherein the arbitrfary point in described method joins hydrogen or steam the raw material of heating.

19. the method for claim 11, wherein the first thermal transition district is fluid coker.

20. the system of the hydrocarbon feed that comprises vacuum residuum for cracking comprises:

21. the system of claim 20, further comprise the second gas/liquid separation be connected with described thermal transition district fluid.

22. the system of claim 20, wherein the first thermal transition district is fluid coker, and described fluid coker comprises:

I) fluidized-bed gasifier,

23. the system of claim 22, further be included in the air/steam entrance of described fluidized-bed gasifier bottom.

24. the system of claim 22, wherein said fluid coker further comprises fluidized-bed well heater container, it has the described well heater container of connection than the recirculated solids pipeline of lower part and described gasifier, with at least one gas pipeline, described gas pipeline the higher part of described gasifier divide and described well heater container than lower part between connect.

25. the system of claim 22, wherein said transfer line reactor is the vertical-lift pipe reactor, wherein said solid pipeline and described hydrocarbon feed entrance be connected to described reactor than lower part.